Utilizing sulfur-containing petroleum.



A C. I. ROBINSON.' UTILIZING SULFUR ooNTAININ'e PETROLEUM.

APPLICATION PILBD`M`AR. 21, 1907. Y

1,018,374. Patented Feb.20,1912.

60005 STILL 50 which is obtained near Beaumont, in 1in.: respect y...to-@both of the characteristics -yherein above mentioned.

CLARENCE I. ROBINSON. F WEST NEW STANDARD OIL COMIEANY, NEW JERSEY.

Original application led August 21, 1903, Serial No'. 170,327. Divided and this application led March 21,

specification o f tetten raten-.

BRIGHTON', -NEW YORK, ASSIG-NOR T0 0F BAYONNE, NEW-JERSEY, A. C QRPURATION 0F UTILIZING sULrUn-coNTAImNe PETROLEUM. l

Patented Feb. 2o, 1912.

1907. 'seriai No. 363,712.

To all 'whom' it may concern:

Be it known that I, CLARENCE I. son, a citizen of theUnited States, at West New Brighton,

Roninresiding in the county' of 5 Richmond and State of New York, have in- State of Texas, near the town of Beaumont,

in JeHerson county. Said petroleum is here? in referred to as Beaumont oil or Beaumont `.petroleum Yfor convenience of reference..

These designations are eachintended to include oil of the same or substantially similar tained.

Forthe purpose of this specification, such substantial similarity4 in character to the oil obtained near Beaumont is Ysuiliciently character .wherever found or however obshown for any crude oil by the fact that it responds to each of the two following tests, that is to say,l first, the sulfur naturally present therein is given off (in utilizable proportion) in the form of hydrogen suld 30., when the crude oil is heated to between about 300 F. and-about500 and, sec-` ond, on distilling the. crude o1l, with or without cracking, and on collecting by itself the fraction coming, over between 250 F.

and 600 F., more or less, the so collected.

distillate, after treatment with sulfuric acid of 66 B. (in however large proportion) and subsequent washing with water and caustic soda lye (all in the known way) will smoke 40 badly when burned in theordinarypetroleum (kerosene) lamps. There may, how-V ever, be petroleum which is analogous to Beaumont oil in responding to the first ofV these tests; but which does not respond to the second of them;' and which consequently is not Beaumont petroleum as'above defined. The invention extends to the utilization of such analogous petroleum as well as of that fwhichgg. is substantially similar to the oil Texas,

I' -:if:Sozfarj. as I ani-aware, naturally-present l 'sulfur hasnever been recovered in utilizable form from any crude petroleum, although it has long been known Ito be a common constituent. of petroleum and to existin considerable proportion in some varieties, as in the oil from the. Lima, Canada, fields, for example. The crude oil from the Pennsylvania .fields is nearly free from it. Beaumont crude oil contains, according to my experience, between one and two per cent of sulfur. Tlie sulfur in Lima or Canadian oil 'is not utilizable as I have found that of Beaumont petroleum to be.

Ohio, and Ontario,

In distilling the former the quantity of sul- I fur in the still gases is too small to `be of use; and it is besides evolved at such times and in such manner that it would be impracticable' to utilize it were the. quantity sufficient.

The utilizable sulfur leum I believe to.exist therein -in elementary state and to for-m hydrogen suliid by its combination at comparatively low temperatures with hydrogen of hydrocarbons, which' are partially decomposed by the sulfur at such temperatures. This. hydrogen sultid comes off, as I have discovered,in large volume during a short period and in such manner that it can be controlled without interfering with the running of the still. Some hydrogen sulid is given off at all timesin distilling crude Beaumont petroleum; but what is evolved at other 'times is not utilizin Beaumont petroi.

able as I have found that which comes ofr' during said short period to be.

In accordance with the present invention Beaumont or analogous oil is heated in a suitable still gradually "to about 500 F.,

more lor less, and the sulfur-containing gas which is given oii' during such rise of temperature (all, or part, as may be determined) is collected, conveyed away and oxidized to form sulfuric acid. This oxidation is effected, first, by combustion in hydrogen sulfid burners, and, second, by subjectionin lead chambers or Contact apparatus to the agencies' necessary to convert sulfur dioxid into sulfuric acid. In this conversion, when it is accomplished inthe lead chambers, the sulfur trioxid unites with water to form chamber acid which. can then be concentrated in anypknown Aor suitable way. Should the conversion be accomplished in contact apparatus, the sulfur trioXid may Lremain free as sulfuric anhydrid (which. is regarded so constitute hydrated' sulfuric acid of temperature of 300 greater or less concentration, fuming or nonfuming, as may be desired. Before the combustion 1n hydrogen suliid burners, the gas should be freed from oil vaporsby cooling. Said epiphustion results in the formation of Water'as well as of sulfur dioXid; and said water may be removed or not before the oxidation of the sulfur dioxid to-sulfuric acid, according to the case. ,Furthen in ac-v cordance with the invention, should it be de sired to utilize the sulfur-containing gas from Beaumont -or analogous crude oil other:

wise than for the preparation lof' sulfuric acid, it can be done by subjecting said gas to any known or suitable procedure for-the utilization of hydrogen sulfid. llbelieve that l am the first" to collect such gas for the utilization of the hydrogen sulid therein.

rllhe heating of the Beaumont oil to obtain the sulfurfbearing gas is best performed at temperatures as nearly constantas is consistent with a good evolution of the sulfurcontaining gas. This evolution is most rapid at from about 400o F. to about 450 F. Especially, therefore, during this temperature interval should the tire be regulated to preserve an even discharge of the gas. By regulating the fire with reference to the sulfur-containing gas, the formation of uncondensable hydrocarbons is reduced, so that, when the gas is burned, the combustion products .will contain but little carbonio oXid and dioxid, freedom from these substances' being desirable for the subsequent conversion of the sulfur dioXid into sulfuricof more than 96% of this substance.

The gas commences to be evolved when the F. is reached (as shown by a thermometer in the liquid in the still). The yield of utilizable gas will,in my experience,have become practically complete when 500 F. is reached.V When the gas evolved becomes (or is at any time found to be) too poor in hydrogen suld or too much mixed with uncondensable hydrocarbons to'be sat isfactorily utilizable, it may be delivered to a pipe line for `burning under the still or be disposed of in any desired way. The heating of the Beaumont oil to obtain utilizable sulfur-containing gas can (and most advantageously does) form part of the distillation for obtaining the burning oil (kerosene) distillate.

Any suitable apparatus can be used to carry out the present invention. rlhe accompanying. drawing is a diagram of such an apparatus. This l have also invented; but in consequence of official requirement of division I'have included it in the subjectmatter of application No. 363,713, -tiled by continuation of remera me on March 21, 1907, as a division and continuation of my application of August, 21, 1903, No.`170,327 and in ,part also as a cony tinuation of my application of the'same date No. 170,326.

Patent 968,692 was granted August 30, 1910, on my 170,327 f and patent 1,014,520 on January 9,

said application No. 4

1912, on my said application No.1170,326. rlhe present application is a division and my said application No. 17 0,327 and has been made in consequence of official requirement of division.

The following is a description of whatis considered thel best mode of carrying the invention into effect. Additions, omissions and otherI modifications can be made indefinitely so long'as the substance of any one or more of the hereinafter written claims 'is taken. The crude Beaumont vpetroleum is supplied after the usual manner to the crude oil still a by a charging line b; and when the still has been lled to the desired level it is heated so as gradually to raise the tempen' 'ature of the stills contents. The gas and vapors as they are formed by theheat pass over ,to the condenser c wherein they are cooled to condense the oil vapors. The liquid of condensation tiovvs into the3 distil-` late receiver d. The gas, including any uncondensed vapor, passes either by the line e to lbe burned as fuel or otherwise disposed of, or by the gas line f to be utilized in sulfurie acid making. While-the temperature of the vapors as they leave the still L is below about 500 F., more or less, the gas from the condenser c consists, of about or above hydrogen sulfid `(ordinarily, if not always) andis'then delivered to gas line The temperature is raised to this degree more gradually than in ordinary distlllation, being regulated with special reference to the production of hydrogen suliid to the best advantage, and the distillate being allowed to take care of itself. lt is specially important to keep the temperature of the'oil as nearly constant as is consistent with a.

good evolution of gas during the temperature intervalfrom about 400 F. 'tol about 450 F., during which interval the evolution of hydrogen sulid is most rapid. By proper regulation 'of the heating, the gas evolved will consist (as is desirable) of a larger proportion of hydrogen sulld and a smaller proportion of uncondensable hydrocarbon vapors than would otherwise be the case.

Should the hydrogen sulid given od atany time below about 500 F. be found to be unsatisfactory in quantity or quality, it can be sent int-o line e as long as it maybe so;'but in my experience this change of gas line has not been found expedient until about 500 F. is reached. At about or above this degree the gas shouldbe turned into the line e., so Soon as the evolution of hydrogen sultd fails lid ' therefrom beyond what can be accomplished by treatment with 66 B. acid and redistillation. vThis has been .found in my experience to be when the gravity of the distillate at the worm end` (that is, before it enters the receiver d), is about 42 B.,`more or less, the temperature of the vapors escaping from the still a being about 400 F., more or less. The distillate then in the receiver 4is hereinafter referred to as the first burning oil out.

oil fraction. It amounts, in my experience, to from five to ten per cent. of the crude oil supplied to still a. The inlet of receiver d is then closed and that of receiver g is opened, so thatA the distillate from condenser c will flow into this latter receiver. This change of receiver has been effected, in my experience, before the yield of hydrogen sulid becomes unsatisfactory; so that for a time after the change of receivers the heat.- ing of the still a is regulated with special reference to the evolution of hydrogen suliid. Afterward theI heat of still a4 is regulated (as customary) with special reference to the distillate to beobtained.

The distillation is carried on with cracking which commences when the temperature of the liquid oil in the still a is about 600 F., more or less, the dis'- tillate in the two receivers d and g then amounting to about 40%, moreor less, of the crude oil supplied to the said still a. The distillation is continued as long as it is bsafe to do so, say, till the distillate in said two .receivers amounts to about 85% of said crude oil. The oil in receiver g is herein termed the cracked oil distillate; although a large percentage is composed of uncracked products.-

Itis customary to have a receiver into which the distillate can be turned whenever it becomes undesirable in quality, the result of something accidental; the receiver h is provided for such purpose. Then necessary, its inlet can be opened, those of the receivers d and g being closed. Any one of the three receivers could be used for this l purpose, the other two serving to collect the rst burning oil cut and the cracked oil distillate, respectively. 'After the completion of a run, the crude oil still a can be emptied through the tar line jor in any suitable way, preparatory to refillinglwith crude oil .for a new run.

The first burning oil cut and the cracked oil distillate may be disposed of as may be desired, the disposition made of them being no part of the present invention. l

f remaining i It belongs to the lighter end of the burning (in my experience) The heating of the crude oil for purposes of the present invention can A(as already indicated) be regarded as complete when the oil in distillation hasattained a temperature of about 500 F.; at which time the supply of elementary sulfur therein will have become practically exhausted. The'natural sulfur content of Beaumont petroleum` is chieiiy in the form 'of elementary sulfur; but it also includes somehydrogen sulfid and some sulfur containingv hydrocarbons. Some sulfur containing hydrocarbons ,are believed also to be formed artificially during distillation ofthe oil. The naturally present hydrogen suliid, of course, unites with that formed artificially. As hydrogen sulfid is soluble in hydrocarbon oils, a certain amount will appear in the distillate. The naturally present and artificially formed sulfur containing hydrocarbons are only to a small extent decomposed on distillation. They, therefore, for the most part either pass v'over with; unsulfured hydrocarbons of like boiling Vpoints and are -condensed with them as part of the distillate, 0r else (if` of too high boiling point to pass over at the temperatures attained) remain in the residual oil.

So much of the gas from the crude stilla as is allowed to enter the gas line f is conveyed thereby toa storage gasometer 3, from which it is supplied to the burner 4, wherein both it and other combustible substances present are burned, the hydrogen sulfid being converted thereby into sulfur dioxid and water.v These ma both be delivered through gas line 5 into the lead chamber 6 for `making sulfuric acid. They could be delivered into a Glover tower 7; but this is not considered desirable, inview of the large proportion of water vapor in admiXt-ure with the Sulfur dioxid. The water could, however, be separated by condensation and the sulfur `dioxid, being heated, could be sent either into tower 7 or lead chamber 6. It could be sent into other sulfuric acid making apparatus.

l'The dilute sulfuric' acid irom the lead.

chamber 6 is carried byline 16 to an apparatus wherein. it is concentrated to any desired degree by heatin lor by addingsulfuric anhydrid or by t e aid of'both-{operations. It is delivered by acid line 18 =to` a storage tank 19 from which it can be discharged through line 20 for sale or use, as may be desired.

The expression operatlons for utilizing the sulfur content inf' those of the hereinafter written claims yin which, it occurs means one or more such operations and refers primarily to operations for converting the sulfur-containing compound into sulfuric acid ;'but it mean.= also other known or suitable operat-ions for utilizing said component. For example, hydrogen sulid can be burned and thefresulting sulfur dioXid utilized in known or suitable ways for producing sulfite and bisulfite salts, sulfurous acid solution and other substances or eects known to be producible by sulfur di- 2. The process of making hydrogen sulfid', by heating sulfur bearing Beaumont or analogous petroleum to .between 300 F. and 500 F., so as to evolve therefrom. a gas rich in hydrogen sulfid and suitably free from non-condensable hydrocarbons, cooling the so evolved gasto separate the condensable hydrocarbons fromY the non-condensable constituents, andcollecting the gas vappropriately for subsequent subjection of the same to operations for utilizing the sul! fur content of hydrogen sulid, substantially as described. v

3. The"k process of making hydrogen sullid, by heating sulfur bearing Beaumont or -analogous petroleumv to temperatures at appropriately v ations for utilizing the sulfur content of which gas rich in hydrogen suld is evolved therefrom, regulating said heating. appropriately forobtaining a steady stream of good volume of non-condensable gas rather than of hydrocarbons condensable as distillate, removing condensable hydrocarbon vapors from said gas, andl collecting thegas for subsequent subjection of the same to operations for utilizing the sulfur'content of said gas, substantially as described.

4. The process of making hydrogen suld, by heating sulfur bearing Beaumont or analogous petroleum tobetween 300 F.

and'500 F., so as to evolve therefrom a gasv rich in hydrogen sulfid and lsuitably free from non-condensable hydrocarbons, cooling the so evolved gas to separate the condensable hydrocarbons from, the non-con- .densable constituents, regulating said heating appropriately frobtaining a steady stream of good volume of the gas ratherthan of the condensate formed by said coolmg subsequent subjection ofthe same to oper- -hydrogen suld, substantially as described.

5. The-process of making hydrogen sulid, by heating sulfur bearing Beaumont or than of hydrocarbons and collecting the gas appropriately for Loiseau.

analogous petroleum to gradually increasing temperatures to evolve gas rich in hydrogen sulfid therefrom, cooling the so evolved gas to separate the condensable hydrocarbons from the non-condensable constituents, collectin the gas appropriately for subsequent subjection of the same to operations for utilizing the sulfur content of hydrogen sulid, and stopping such collection when the temperature of the so heated petroleum is about 500 F., substantially as descri f 6. he process of utilizing Beaumont or analogous petroleum, by heating such sulfur bearingpetroleum to temperatures at which gas rich in hydrogen sulfid is evolved therefrom, removing condensable hydrocarbon vapors from the so evolved gas, collecting ther remaining gas, and subjecting it to operations for'utilizing the sulfur content of said gas, substantially as described. 7. The process of utilizingBeaumont or analogous petroleum, by heating such sulful bearing petroleum to between 300"v F. and 500 F., so as to evolve therefrom gas rich in hydrogen sulfid and suitably free from noncondensable hydrocarbons, cooling the so evolved gas to separate the condensable hydrocarbons from the,.non-con 4densable constituents, collecting the gas, and

subjecting it to 'operations for utilizing the sulfur content of hydrogen sulid, substantially as described. j

S. The process of utilizing Beaumont or analogous petroleum, by heating such sulfur bearing petroleum to vtemperatures at which gas rich in4 hydrogen sulid is evolved therefrom, regulating 'said heat-ing appropriately for obtaininga steady stream of goodvolume of non-condensable gas rather condensable as distillate, removing condensable hydrocarbon vapors from said gas, collecting the gas, and subjecting it to operations for utilizing the sulfur content of said gas, substantially as described.

9. The process of utilizing Beaumont or analogous petroleum, by heating such sulfur bearing petroleum to between 300 F. and 500 F., so as to evolve therefrom a gas rich in hydrogen sulfid and suitably free from non-condensable hydrocarbons, cooling the so evolved gas to separate the condensable hydrocarbons from the non-condensable constituents, regulating said heating appropriately for obtaining a steady stream of good volume of the gas rather than of the condensate formed by said cooling, collecting the gas, and subjecting it to operations for utilizing the sulfur content of hydrogen suliid, substantially as described.

10. The process of'utilizing Beaumont or analogous petroleum, by heating such sul- -fur bearing petroleum to gradually increasdrogen sulfid therefrom, cooling the so evolved gas to separate the condensable hyjection of the gas to said/operations when,

the temperature of the so heated petroleum is about 500 F., substantially as described.

11. The process of separating certain sulfur and hydrocarbon constituents of Beaumont or analogous petroleum from each other, by heating such sulfur bearing petroleum to temperatures at which gas rich in hydrogen sulid is evolved therefrom, and regulating said heating appropriately for obtaining a steady stream of good volume of non-condensable gas rather than of condensable hydrocarbons, substantially as described.

12. The process of separating certain sulfur and hydrocarbon constituents of Beaumont or analogous petroleum from each other, by heating such sulfur bearing troleum to between 300 F. and 500 F., and regulating said heating appropriately for obtaining a steady stream of good vo ume of non-condensable gas rather than of condensable hydrocarbons, described.

substantially as 13. -The process of/separat-ing'certain sulfur and hydrocarbon constituents of Beaumont or' analogous petroleum vfrom each other,'by heating such sulfur bearing peltroleum to temperatures at which gas rich in hydrogen sulid is evolved therefrom, regulating said heat-ing appropriately for vobtaining a steady stream of good volume.

'fur and hydrocarbon constituents of Beaumont or analogous petroleum from each p other, by heating such sulfur bearing petroleum to between 300 F. and 500 F., regulating said heating appropriately for ob` taining a steady stream of good volume of non-condensable gas rather than of con,-

densable hydrocarbons', and removing condensable hydrocarbon vapors from said gas, substantially als described.

In testimony whereof I allx my signa' ture, in presence of twowitnesses,I

I CLARENCE I. ROBINSON.

Witnesses:

LEE ToADvINE, A. P. ,ARNoL'm 

